Quaternary ammonium compounds and method for their manufacture

ABSTRACT

Quaternary ammonium compounds having the general formula: ##STR1## wherein m is either 0, 1, 2, or 3; each R 5  may be the same or different and are selected from the groups including straight- or branched-chain alkyl or alkenyl radicals having from 1 to 30 carbon atoms, inclusive, or a phenyl or benzyl radical; R 2  is H-, a C 1  to C 10  straight- or brached-chain alkyl or alkenyl radical, a phenyl group, a benzyl group, or a halogenated alkyl group; R 3  and R 4  are different or the same and are selected from the group including H-, or a C 1  to C 10  straight- or branched-chain alkyl or alkenyl radical, a phenyl group, or a benzyl group, and wherein n is an integer between 0 and 30, inclusive, and methods for their manufacture are described.

BACKGROUND OF THE INVENTION

The present invention relates to the preparation of novel quaternaryammonium compounds and particularly to alkoxylated quaternary ammoniumalkylene glycol borate esters and methods for their preparation. Thepresent compounds are alkoxylated at at least one and up to three of thequaternary nitrogen bonding sites.

The manufacture of alkoxylated quaternary ammonium alkylene glycolborate esters is unknown, although compounds comprised of an inorganiccation or an alkyl quaternary cation and this anion are known. Examplesof such compounds include the sodium salt of a boric acid cyclicphenylethylene ester disclosed by Bell in the Australian Journal ofChemistry, volume 23, issue 7 (1970), pages 1415-1420 (Chem. Abstractsreference 65954r); and the quaternary ammonium glycol monoborate saltsdisclosed by Hunter in U.S. Pat. No. 3,169,983, issued Feb. 16, 1965.

The present alkoxylated quaternaries are found to be useful in themanufacture of polyurethane foams. In several U.S. Patents, includingU.S. Pat. Nos. 3,661,809; 3,726,816; and 4,256,802, urethanes aremanufactured by blending two components, stirring, and then allowing theblend to rise in an open container so as to form the desired foam. Thesetwo components are known as the "A" and "B" components, with the "A"component comprising the isocyanate and the "B" component comprising ablend of polyol, catalyst, surfactant, and blowing agent. All of themethods of polyurethane foam manufacture disclosed in the above patents,however, require that a conventional catalyst, such as an alkali metalsalt, be used.

SUMMARY OF THE INVENTION

The present compounds are quaternary ammonium compounds having theformula: ##STR2## wherein R₁ is a straight- or branched-chain alkyl oralkenyl radical having from 1 to 30 carbon atoms, inclusive, or a phenylor benzyl radical; R₂ is H-, a C₁ to C₁₀ straight- or branched-chainalkyl or alkenyl radical, a phenyl group, a benzyl group, or ahalogenated alkyl group; R₃ and R₄ are different or the same and areselected from the group including H-, or a C₁ to C₁₀ straight- orbranched-chain alkyl or alkenyl radical, a phenyl group, or a benzylgroup, and wherein n is an integer between 0 and 30, inclusive, andmethods for their manufacture are described.

In yet another embodiment of the invention, the alkylene glycol borateester anion depicted hereinabove is coupled with the cationic moiety:##STR3## wherein m is either 0, 1, 2, or 3; each R₅ may be the same ordifferent and are selected from the groups including straight orbranched-chain alkyl or alkenyl radicals having from 1 to 30 carbonatoms, inclusive, or a phenyl or benzyl radical; R₂ is H-, a C₁ to C₁₀straight- or branched-chain alkyl or alkenyl radical, a phenyl group, abenzyl group, or a halogenated alkyl group, and wherein n is an integerbetween 0 and 30, inclusive.

In another embodiment, the ethylene glycol borate ester anion depictedhereinabove is coupled with the cationic moiety: ##STR4## wherein n andR₂ are as defined hereinabove, t is either 1, 2, or 3, R₆ is a C₁ -C₂₀alkyl or alkoxy group, and R₇ is a C₂ or C₃ alkyl group. Preferably, R₇is --C₃ H₆ -- and R₆ is a combination of approximately equal amounts ofC₁₂ -C₁₅ alkyl groups.

The above compounds may be manufactured by a process in which boric acidis blended with an alkylene glycol, and then heating the blend. Thewater produced in the reaction is stripped off in successive atmosphericand vacuum distillation steps. Preferably, enough water is removed sothat no more than 0.2% by weight remains in the alkylene glycol borateester formed in the reaction. The dried borate ester is added to aprimary, secondary, tertiary, or ether amine to form an aminatedalkylene glycol borate ester. Finally, this aminated borate ester isalkoxylated with an alkylene oxide in the presence of a solvent.

The reaction of the glycol and boric acid may be represented as follows:##STR5##

When the above ester is reacted with an amine, as for example a primaryamine and 3 moles of ethylene oxide, ##STR6## The remaining portion ofthe originally formed borate ester is cleaved away from the anionicportion and forms an alkylene oxide.

Accordingly, R₃ and R₄ in the present compounds may be modified byappropriate use of glycols in the first reaction with boric acid. Forexample, to attain the present compound wherein R₃ is H- and R₄ is C₈ -,one should react 2 moles of 1,2-dihydroxy decane with a mole of boricacid.

For secondary amines, where n=0, 2 moles of the alkylene oxide are addedper mole of amine. For n>0, the moles of alkylene oxide added will be2(n+1) per mole of amine.

For any primary, secondary, or tertiary amine not having a hydroxyalkylgroup thereon, and where n and m are as defined above, the requiredmoles of alkylene oxide used will be moles alkylene oxides=(n+1)(4-m),as will be recognized by those skilled in the art.

A still further embodiment of this invention is a method as disclosedabove wherein the molar ratio of the alkylene glycol to boric acid isbetween 1:1 and 3:1. In another embodiment, the solvent comprises from5% to 20% of the combined weight of all of the reactants, that is, thesolvent, boric acid, alkylene glycol, amine, and alkylene oxide. Inother embodiments, the molar ratio of the amine to the alkylene glycolborate ester is 1:1, and the solvents are selected from the groupincluding diethylene glycol and ethylene glycol.

Suitable alkylene glycols may be selected from the group includingethylene glycol and propylene glycol. Further, it will be appreciated bythose skilled in the art that any alkanol or other hydroxy-containingcompound may be combined with boric acid to form a similar borate ester.Some suitable primary amines include tallowamine, 3-alkoxypropylamine,cocoamine, dodecylamine, and hexadecylamine. Secondary amines, amongothers, may be selected from the group includingdi(hydrogenatedtallow)amine and dicocoamine. Examples of some suitabletertiary amines are N-methyl diethanolamine, triethyl amine,dimethylethanolamine, and N,N-dimethyldodecyl-amine. Alkylene oxides mayinclude ethylene oxide, propylene oxide, styrene oxide (for R₂ ═C₆ H₅),3-phenyl-1,2 propylene oxide (for R₂ ═C₆ H₅ CH₂ --), and4,4,4-trichloro-1,2-butylene oxide (for R₂ as a halogenated alkylgroup), and suitable solvents include diethylene glycol, dipropyleneglycol, ethylene glycol, 2-ethylhexanol, and any other alkanol, such asisopropyl alcohol, ethanol, and methanol.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present compounds may be manufactured using equipment commonlyavailable to those who manufacture conventional quaternary ammoniumcompounds.

The preferred method comprises charging an alkylene glycol and boricacid to a reactor, preferably including a distilling column upon whichvacuum may be drawn. The glycol borate ester blend is heated to 120° C.at atmospheric pressure, and water will begin boiling off of thewater-borate ester blend. Vacuum of 15-20" Hg is placed upon the columnand a small amount of nitrogen is introduced into the reactor, both toassist in the removal of any remaining water. When the rate ofdistillation slows, the reactor is slowly returned to atmosphericpressure. Care should be taken not to use excessive vacuum, as thealkylene glycol borate ester boils at 120° C. at an absolute pressure of1.5 to 2.0 mm Hg. The dried product is analyzed for water, and thedistillation steps repeated until the water content is at or below 0.2%.The amine and the solvent are then transferred to an autoclave, as forexample a Carpenter 20 autoclave, communicative with an alkylene oxidereservoir. The borate ester is added slowly, resulting in an exothermicreaction. The reactor is cooled so as to maintain the contents at from75° C. to 85° C., and purged three times with nitrogen in successivepressure-vent cycles. The vent is then closed, and the reactor chargedwith nitrogen to 7 psig.

The alkylene oxide is then added with the reactor contents at 75° C. to85° C. and at a rate such that the reactor pressure does not exceed 50psig. When all of the alkylene oxide is charged, digestion thereof isallowed until the reactor pressure drops to 20-25 psig.

A conventional analysis of the total milliequivalents per gram (meq/g)of quat and free amine in the reaction mixture is then made. The"percent conversion" is defined as: ##EQU1## If this percent conversionis less than 70%, additional alkylene oxide is added until the percentconversion exceeds 70%.

A Karl-Fischer water analysis is obtained on the remaining quat/freeamine blend. If the water content is less than 0.1%, the reactor isvented, cooled to 75° C., and the reaction mixture removed therefrom.The resulting mixture primarily contains a compound in accordance withthe present invention.

If the amount of water exceeds 0.1%, the reactor should be vented to 0psig, then purged with nitrogen at a rate of 1.5 standard cubic feet perhour (1.5 SCFH) per pound of batch weight, maintaining the reactor at100° C. This procedure is continued and the water content checked everytwo hours until it drops below 0.1% or until three consecutive analysesshow no change. Finally, the reactor is vented, cooled to 75° C., andthe contents discharged. The contents are primarily a compound inaccordance with the present invention.

Specific examples are listed hereinbelow, which are the preferredmethods of manufacturing the cited compounds in accordance with theabove general procedure.

EXAMPLE 1

327 grams (5.27 gram moles) of ethylene glycol was added to 163 grams(2.63 gram moles) of boric acid in a one-liter, three neck flaskequipped with a heating mantle, a Dean Stark trap, and a condenser. Themixture was heated to 120° C. at atmospheric pressure. After heating themixture for about 1 hour 45 minutes at temperatures between 120° and129° C., during which time about 45 grams of water was stripped off ofthe blend, a water aspirator was started so as to create a slight vacuumat the condenser. During the next three hours, a total of 83.4additional grams of water were stripped for a total of 124.5 grams or6.92 gram moles, which is 87.7% of the theoretical amount of 7.89 grammoles (3 moles water per mole boric acid). One hundred and seventy three(173) grams of the resulting adduct shown at Formula (I) was added to327.7 grams (1.246 moles) of Armeen® TMD aliphatic amine in a 1 literParr Carpenter 20 autoclave (hereinafter "reactor"). Armeen® TMDaliphatic amine is available from the Armak Company, IndustrialChemicals Division, 300 South Wacker Drive, Chicago, Ill. 60606, and iscommonly known as distilled grade tallowamine. After the amine andborate ester were blended, the autoclave was twice purged with nitrogenat 50 psig.

The reactor is communicative with an ethylene oxide reservoir through astainless steel tube. Ethylene oxide, pressured in its reservoir bynitrogen, is slowly added to the reactor over the next 16 hours, atwhich time the reactor is at a pressure of 25 psig and 7.0 gram moles ofethylene oxide have been added. The resulting product is a ethoxylatedquaternary ammonium ethylene borate ester having the formula: ##STR7##the C₁₈ H₃₇ in the above-formula representing the primarily eighteencarbon tallow alkyl grouping. Upon analysis, the reaction mix was foundto contain 3.5% free amine, 69.4% quaternary ammonium borate ester, and1.2% water.

EXAMPLE 2

1500 grams of ethylene glycol (24.2 moles) were blended with 746.7 gramsof boric acid (12.1 moles) to yield the borate ester shown at formula(I). The mixture was heated to 135° C. under slight vacuum so as toremove water therefrom, as in Example 1. To 134 grams of this borateester (1.01 gram moles) in a reactor was added 265.6 grams (1.01 grammoles) of Armeen® T. Armeen® T is a product of the Armak Company,Industrial Chemicals Division, 300 South Wacker Drive, Chicago, Ill.,60606, and is commonly known as technical grade tallowamine. 252.5 grams(5.74 gram moles) of ethylene oxide are added at 50 psig and 75° C. overthe next 81/2-9 hours after the addition of 72.5 grams of diethyleneglycol (a solvent), added so as to comprise 10% of the combined weightof the amine, the ethylene glycol borate ester, the ethylene oxide, andthe solvent. The resulting product is that set forth above at formula(II). Analysis indicates that 24.3% of the reaction mixture is presentas a free amine, whereas 39.0% of the mixture is a quaternized compound.

EXAMPLE 3

304 grams of 1,2-propane diol (4.0 gram moles) are added to 124 grams ofboric acid (2.0 gram moles) in a one-liter, three neck flask equippedwith a heating mantle, a Dean Stark trap, and a condenser. The mixtureis heated to 128° C. at atmospheric pressure, and retained there forabout 31/2 hours, during which time about 44.5 grams of water arestripped from the mixture. A water aspirator is then started so as tocreate a slight vacuum at the condenser, and another 65.0 grams of wateris stripped from the mixture during the next 53/4 hours. The total waterremoved of 109.5 grams corresponds to the stoichiometrical amount, butanalysis of the adduct remaining in the flask showed that it contained3.4% water.

160 grams (1.0 gram mole) of this propylene glycol borate ester areadded to 262 grams (1.0 gram mole) of Armeen® TMD aliphatic amine and134 grams (1.0 gram mole) of dipropylene glycol, a solvent. The reactorin which these reactants are blended is communicative with an ethyleneoxide reservoir through a stainless steel tube. Four moles of ethyleneoxide, pressurized in its reservoir by nitrogen, are slowly added to thereactor over the next 81/2 hours, and the resulting quaternary isrepresented by the formula: ##STR8## The product formed in the aboveethoxylation comprises 48.6% of the ethoxylated quaternary ammoniumborate ester shown above and 10.3% free amine.

EXAMPLE 4

Propylene glycol borate ester was prepared in accordance with theprocedures set forth in the first paragraph of Example 3 hereinabove.131.8 grams (0.824 gram moles) of this borate ester were blended with230.1 grams (0.824 gram moles) of Armeen® EA 25 aliphatic amine and 40.9grams diethylene glycol in a one liter, Carpenter 20 Parr autoclave.Armeen® EA 25 aliphatic amine is 3-alkoxypropylamine, and is availablefrom the Armak Company. It is an ether monoamine made from an alcoholmixture comprised mainly of C₁₂ -C₁₅ alcohols, approximately equalamounts of all chain lengths being present. The autoclave iscommunicative with an ethylene oxide reservoir through a stainless steeltube. After heating the reaction mixture to 72° C., 4.12 gram moles ofethylene oxide are added thereto over the next six hours. Upon analysis,the product formed by the ethoxylation proved to be: ##STR9## wherein R₅comprises mainly C₁₂ -C₁₅ alkyl groups, approximately equal amounts ofall chain lengths being present. The final reaction mixture contained2.0% free amine, 57.3% quaternary ammonium borate ester, and 0.5% water.

EXAMPLE 5

Ethylene glycol borate ester was prepared in accordance with theprocedures set forth in the first paragraph of Example 1 hereinabove.225.6 grams (1.70 gram moles) of this borate ester, 200 grams (1.70 grammoles) of N-methyl diethanol amine, a tertiary amine, and 143.8 grams ofdiethylene glycol are added to an autoclave that is communicative withan ethylene glycol reservoir through a stainless steel tube. Over thenext five hours, 149.6 grams (3.40 gram moles) of ethylene oxide areadded to the mixture in the autoclave, and the reaction mixture is thencooled and analyzed. Only 0.24% water remains in the quaternary ammoniumborate ester. The resulting quaternary ammonium ethylene glycol borateester has the structure: ##STR10##

EXAMPLE 6

Propylene glycol borate ester was prepared in accordance with theprocedures set forth in the first paragraph of Example 3 hereinabove.240.0 grams (1.50 gram moles) of this borate ester were blended in aone-liter, Carpenter 20 Parr autoclave with 151.8 grams (1.50 grammoles) triethyl amine and 92.2 grams of diethylene glycol, a solvent.The diethylene glycol is added in an amount sufficient so that it willcomprise 15% of the total weight of solvent, borate ester, amine, andpropylene oxide. After heating the reaction mixture to 75° C., propyleneoxide is added slowly thereto until 130.7 grams (2.25 gram moles) havebeen added in six hours. Analysis of the resulting reaction mixturedisclosed a compound having the formula: ##STR11## The reaction mixturehas a moisture of 0.14%.

EXAMPLE 7

Propylene glycol borate ester was prepared in accordance with theprocedures set forth in the first paragraph of Example 3 hereinabove.240.0 grams (1.50 gram moles) of this borate ester were blended in aone-liter, Carpenter 20 Parr autoclave with 151.8 grams (1.50 grammoles) triethyl amine and 80.7 grams of diethylene glycol, a solvent.This blend is heated to 75° C., and ethylene oxide is added slowlythereto until 66.0 grams (1.50 gram moles) have been added over 41/2hours. Analysis of the resulting reaction mixture disclosed a compoundhaving the formula: ##STR12## The product had a moisture content of0.48%.

EXAMPLE 8

Propylene glycol borate ester was prepared in accordance with theprocedures set forth in the first paragraph of Example 3 hereinabove.Eighty grams (0.5 gram moles) of this propylene glycol borate ester wasblended with 131 grams (0.5 gram moles) of Armeen® TMD aliphatic amineand 26 grams of dipropylene glycol, a solvent, in a one liter, Carpenter20 Parr autoclave. After heating the reaction mixture to 75° C., 2.0gram moles (88 grams) of ethylene oxide are added thereto over the next41/2 hours. The resulting reaction mixture proved upon analysis tocontain 53.4% of a quaternary, 9.7% free amine, and 1.0% water. Thequaternary was of the formula: ##STR13##

EXAMPLE 9

Propylene glycol borate ester was prepared in accordance with theprocedures set forth in the first paragraph of Example 3 hereinabove.Ninety five grams (0.63 moles) of this propylene glycol borate esterwere blended with 125 grams (0.63 moles) of Armeen® C aliphatic amineand 25 grams of ethylene glycol, a solvent, in a one-liter Carpenter 20Parr autoclave. Armeen® C aliphatic amine is the trademark of the ArmakCompany, Industrial Chemicals Division, for cocoamine. After heating thereaction mixture to 75° C., 3.15 gram moles (138.6 grams) of ethyleneoxide are added thereto over the next 83/4 hours. Analysis of theresulting reaction mixture disclosed the presence of 3.4% free amine,1.2% water, and 61.8% of an ethoxylated quaternary propylene glycolborate ester having the general formula: ##STR14##

EXAMPLE 10

Propylene glycol borate ester was prepared in accordance with theprocedures set forth in the first paragraph of Example 3 hereinabove.One hundred and fifty grams (1.0 gram mole) of this borate ester wereblended with 262 grams (1.0 gram mole) of Armeen® TM 97 aliphatic amineand 52.4 grams of ethylene glycol, a solvent, in an autoclave. Armeen®TM 97 is the trademark for Armak's tallowamine, 97% primary amine. Afterheating the reaction mixture to 75° C., 5.0 gram moles (220 grams) ofethylene oxide are added thereto over the next 63/4 hours. The resultingreaction mixture proved upon analysis to contain 4.9% free amine and57.4% of the quaternary having the formula: ##STR15##

EXAMPLE 11

Propylene glycol borate ester was prepared in accordance with theprocedures set forth in the first paragraph of Example 3 hereinabove.94.4 grams (0.59 gram moles) of this borate ester were blended with 300grams (0.59 gram moles) of Armeen® 2HT aliphatic amine, so as to obtaina 1:1 molar ratio of amine to borate ester, and 39.4 gram moles ofdiethylene glycol, a solvent. Armeen® 2HT is the Armak Company'strademark for di(hydrogenated)tallowamine, a secondary amine. Afterheating the reaction mixture to 75° C., 2.95 gram moles (129.8 grams) ofethylene oxide are added thereto over the next 121/2 hours. Analysis ofthe resulting mixture showed a blend containing 21.4% free amine and65.5% quaternary ammonium borate ester having the formula: ##STR16##

EXAMPLE 12

Propylene glycol borate ester was prepared in accordance with theprocedures set forth in the first paragraph of Example 3 hereinabove.134.4 grams (0.84 gram moles) of this propylene glycol borate ester wereblended with 225 grams (1.125 gram moles) of Armeen® C aliphatic amine,so as to obtain a 1:0.75 molar ratio of amine to borate ester, and 40.9grams of diethylene glycol, a solvent, in an autoclave. After heatingthe reaction mixture to 75° C., 184.8 grams (4.2 gram moles) of ethyleneoxide are added, thereto over the next 51/4 hours. Analysis of theresulting mixture showed a blend containing 25.3% free amine and 48.5%quaternary ammonium borate ester having the formula: ##STR17##

EXAMPLE 13

Propylene glycol borate ester was prepared in accordance with theprocedures set forth in the first paragraph of Example 3 hereinabove.62.4 grams (0.39 gram moles) of this borate ester were blended with 400grams (0.78 gram moles) of Armeen® 2HT aliphatic amine, so as to obtaina 1:0.5 molar ratio of amine to borate ester, and 41.3 grams ofdiethylene glycol, a solvent. After heating the reaction mixture to 75°C., 85.8 grams (1.95 gram moles) of ethylene oxide are added theretoover the next 41/2 hours. Analysis of the resulting mixture showed ablend containing 40.1% free amine and 57.2% of a quaternary ammoniumborate ester having the formula: ##STR18##

EXAMPLE 14

Propylene glycol borate ester was prepared in accordance with theprocedures set forth in the first paragraph of Example 3 hereinabove. 40grams (0.25 gram moles) of this borate ester were blended with 262 grams(1.0 gram mole) of Armeen® TM 97 aliphatic amine, so as to obtain a1:0.25 ratio of amine to borate ester, and 58.1 grams of diethyleneglycol, a solvent. After heating the reaction mixture to 75° C., 121.0grams (2.75 gram moles) of ethylene oxide are added thereto over thenext 21/2 hours. Analysis of the resulting mixture showed a blendcontaining 45.4% free amine and 36.7% of a quaternary ammonium propyleneglycol borate ester having the formula: ##STR19## The results ofExamples 11-14 are summarized in the following Table I:

                  TABLE I                                                         ______________________________________                                        CONVERSION TO QUATERNARY AMMONIUM                                             COMPOUND USING VARIOUS MOLE RATIOS                                            OF AMINE:PROPYLENE GLYCOL BORATE ESTER.                                                            MOLE                                                                          RATIO,                                                                        AMINE:      WT. RATIO,                                                        BORATE      QUAT:                                        EXAMPLE  AMINE USED  ESTER       FREE AMINE                                   ______________________________________                                        11       di(hydrogenated                                                                           1:1         65.5:21.4                                             tallow)amine                                                         12       cocoamine   1:0.75      48.5:25.3                                    13       di(hydrogenated                                                                           1:0.50      57.2:40.1                                             tallow)amine                                                         14       tallowamine 1:0.25      27.4:67.6                                    ______________________________________                                    

EXAMPLE 15

320 grams (2.0 gram moles) of the propylene glycol borate ester preparedin accordance with the procedures set forth in the first paragraph ofExample 3 hereinabove were blended with 178.3 grams (2.0 gram moles) ofdimethylethanolamine and 35.7 grams of diethylene glycol, a solvent.After heating the reaction mixture to 75° C., 176.0 grams (4.0 grammoles) of ethylene oxide were added to the mixture over the next 6 hours5 minutes. The resulting mixture proved upon analysis to contain 0.34%water, and an ethoxylated quaternary ammonium propylene glycol borateester having the formula: ##STR20##

EXAMPLE 16

160 grams (1.0 gram mole) of the propylene glycol borate ester preparedin accordance with the procedures set forth in the first paragraph ofExample 3 hereinabove were blended with 178.3 grams (2.0 gram moles) ofdimethylethanolamine and 81.6 grams of diethylene glycol, a solvent.After heating the 16.1% (wt.) solvent-containing reaction mixture to 75°C., 88.0 grams (2.0 gram moles) of ethylene oxide were added to themixture over the next 3 hours 20 minutes. The resulting mixture provedupon analysis to contain 0.05% water and the quaternary shown at Example15.

EXAMPLE 17

In contrast to the above procedures, 74 grams (1.19 gram moles) of boricacid (H₃ BO₃) was blended with 250 grams (0.95 gram moles) of Armeen®TMDand 100 grams of 2-ethylhexanol, a solvent. After heating the reactionmixture to 75° C., 209.2 grams of (4.75 gram moles) of ethylene oxideare added thereto over the next 12 hours 20 minutes. The resultingmixture proved upon analysis to contain 9.02% water. After 14 hours ofdistillation, this compound had a moisture content well in excess of0.1%.

The manufacture of polyisocyanurate foams generally require catalysts,such as alkali metal salts, for the reaction to proceed normally.Surprisingly, the addition of the present compounds as co-polyols inpolyisocyanurate and polyurethane foam manufacture eliminates the needfor conventional catalysts. Further, the hydroxyl content of the presentcompounds reduces the need for a conventional polyol.

EXAMPLE 18

Thirteen (13.0) grams of the ethoxylated quaternary ammonium compoundmanufactured in accordance with the procedures at Example 12 were addedto 120 grams of Voranol 575, a polyether polyol available from the DowChemical Company, Midland, Mich.; 2.7 grams of DC-193, a surfactanthaving silicone glycol copolymers with direct silicone-carbon bonds, andsold by the Dow Corning Corporation, Midland, Mich.; 54.0 grams of Freon11A, a trifluorochloromethane available from E. I. DuPont de NemoursCompany, Wilmington, De.; and 210 grams of Mondur MR, a polycyclicaromatic polyisocyanate available from the Mobay Chemical Corporation,Pittsburgh, Pa., and a polyurethane foam resulted. The blend had anNCO/OH ratio of 1.07, a cream time of 18 seconds, a gel time of 30seconds, a rise time of 33 seconds, and a tack-free time of 37 seconds.No conventional catalyst was needed or used, and the resulting foamexhibited good physical properties.

EXAMPLE 19

Six and seven-tenths (6.7) grams of the ethoxylated quaternary ammoniumcompound manufactured by substituting tallowamine for the cocoamine inExample 12 were added to 126.3 grams of Voranol 575, 2.7 grams ofDC-193, 54.0 grams of Freon 11A, and 213.9 grams of Mondur MR, and apolyurethane foam resulted. The blend had an NCO/OH ratio of 1.05, acream time of 27 seconds, a gel time of 55 seconds, a rise time of 1minute, and a tack-free time of 63 seconds. No conventional catalyst wasneeded or used, and the resulting foam exhibited good physicalproperties.

EXAMPLE 20

Thirteen (13.0) grams of the ethoxylated quaternary ammonium compound ofExample 19 were added to 120 grams of Voranol 575, 2.7 grams of DC-193,54.0 grams of Freon 11A, and 212.9 grams of Mondur MR, and apolyurethane foam resulted. The blend had an NCO/OH ratio of 1.05, acream time of 22 seconds, a gel time of 37 seconds, a rise time of 39seconds, and a tack-free time of 44 seconds. No conventional catalystwas needed or used, and the resulting foam exhibited good physicalproperties.

EXAMPLE 21

Six and seven-tenths (6.7) grams of the ethoxylated quaternary ammoniumcompound manufactured by substituting tallowamine for thedi(hydrogenated tallow)amine in Example 13 were added to 126.3 grams ofVoranol 575, 2.7 grams of DC-193, 54.0 grams of Freon 11A, and 212.9grams of Mondur MR, and a polyurethane foam resulted. The blend had anNCO/OH ratio of 1.05, a cream time of 31 seconds, a gel time of 58seconds, a rise time of 62 seconds, and a tack-free time of 72 seconds.No conventional catalyst was needed or used, and the resulting foamexhibited good physical properties.

EXAMPLE 22

Thirteen (13.0) grams of the ethoxylated quaternary ammonium compound ofExample 21 were added to 120 grams of Voranol 575, 2.7 grams of DC-193,54.0 grams of Freon 11A, and 210.7 grams of Mondur MR, and apolyurethane foam resulted. The blend had an NCO/OH ratio of 1.05, acream time of 24 seconds, a gel time of 40 seconds, a rise of 41seconds, and a tack-free time of 50 seconds. No conventional catalystwas needed or used, and the resulting foam exhibited good physicalproperties.

EXAMPLE 23

Six and seven-tenths (6.7) grams of the ethoxylated quaternary ammoniumcompound manufactured in accordance with the procedures at Example 14were added to 126.3 grams of Voranol 575, 2.7 grams of DC-193, 54.0grams of Freon 11A, and 210 grams of Mondur MR, and a polyurethane foamresulted. The blend had an NCO/OH ratio of 1.08, a cream time of 31seconds, a gel time of 62 seconds, a rise time of 66 seconds, and atack-free time of 81 seconds. No conventional catalyst was needed orused, and the resulting foam exhibited good physical properties.

EXAMPLE 24

Thirteen (13.0) grams of the ethoxylated quaternary ammonium compound ofExample 14 were added to 120 grams of Voranol 575, 2.7 grams of DC-193,54.0 grams of Freon 11A, and 209 grams of Mondur MR, and a polyurethanefoam resulted. The blend had an NCO/OH ratio of 1.09, a cream time of 24seconds, a gel time of 48 seconds, a rise time of 52 seconds, and atack-free time of 62 seconds. No conventional catalyst was needed orused, and the resulting foam exhibited good physical properties.

EXAMPLE 25

Six and seven-tenths (6.7) grams of the ethoxylated quaternary ammoniumcompound manufactured in accordance with the procedures at Example 10were added to 120.3 grams of Voranol 575, 2.7 grams of DC-193, 54.0grams of Freon 11A, and 210 grams of Mondur MR, and a polyurethane foamresulted. The blend had an NCO/OH ratio of 1.05, a cream time of 29seconds, a gel time of 46 seconds, a rise time of 49 seconds, and atack-free time of 54 seconds. No conventional catalyst was needed orused, and the resulting foam exhibited good physical properties.

EXAMPLE 26

Thirteen (13.0) grams of the ethoxylated quaternary ammonium compoundmanufactured in accordance with the procedures at Example 12 were addedto 120 grams of Voranol 575, 2.7 grams of DC-193, 54.0 grams of freon11A, and 210 grams of Mondur MR, and a polyurethane foam resulted. Theblend had an NCO/OH ratio of 1.05, a cream time of 19 seconds, a geltime of 27 seconds, a rise time of 28 seconds, and a tack-free time of35 seconds. No. conventional catalyst was needed or used, and theresulting foam exhibited good physical properties.

What we claim is:
 1. A quaternary ammonium compound having the formula:##STR21## wherein R₁ is a straight- or branched-chain alkyl or alkenylradical having from 1 to 30 carbon atoms, inclusive, or a phenyl orbenzyl radical; R₂ is H--, a C₁ to C₁₀ straight- or branched-chain alkylor alkenyl radical, a phenyl group, a benzyl group, or a halogenatedalkyl group; R₃ and R₄ are different or the same and are selected fromthe group including H--, or a C₁ to C₁₀ straight- or branched-chainalkyl or alkenyl radical, a phenyl group, or a benzyl group, and whereinn is an integer between 0 and 30 inclusive, said quaternary ammoniumcompound having a water content not greater than 1.2 percent.
 2. Thecompound as set forth in claim 1, wherein R₁ is a straight- orbranched-chain alkyl or alkenyl radical having from 8 to 18 carbonatoms, and R₂ is H--.
 3. The compound as set forth in claim 1, whereinR₃ and R₄ are H--.
 4. The compound as set forth in claim 1, wherein R₃is H-- and R₄ is CH--.
 5. The compound as set forth in claim 3, whereinn is
 0. 6. The compound as set forth in claim 4, wherein n is
 0. 7. Thecompound as set forth in claim 5, wherein R₁ is C₁₈ H₃₇ --.
 8. Thecompound as set forth in claim 6, wherein R₁ is C₁₂ H₂₅ --.
 9. Aquaternary ammonium compound having the formula: ##STR22## wherein m iseither 0, 1, 2, or 3; each R₅ may be the same or different, and areselected from the groups including straight or branched-chain alkyl oralkenyl radical having from 1 to 30 carbon atoms, inclusive, or a phenylor benzyl radical; R₂ is H--, a C₁ to C₁₀ straight- or branched-chainalkyl or alkenyl radical, a phenyl group, a benzyl group, or ahalogenated alkyl group; R₃ and R₄ are different or the same and areselected from the group including H--, or a C₁ to C₁₀ straight- orbranched-chain alkyl or alkenyl radical, a phenyl group, or a benzylgroup, and wherein n is an integer between 0 and 30, inclusive, saidquaternary ammonium compound having a water content not greater than 1.2percent.
 10. The compound as set forth in claim 9, wherein R₅ is astraight-chain alkyl radical having from 1 to 18 carbon atoms.
 11. Thecompound as set forth in claim 10, wherein m is 2, and n is 0, and R₂ isH--.
 12. The compound as set forth in claim 10, wherein m is 3, each R₅is CH₃ CH₂ --, n is 0, and R₂ is CH₃ --.
 13. A quaternary ammoniumcompound having the formula: ##STR23## wherein t is either 1, 2, or 3,R₂ is H--, a C₁ to C₁₀ straight- or branched-chain alkyl or alkenylradical, a phenyl group, a benzyl group, or a halogenated alkyl group;R₃ and R₄ are different or the same and are selected from the groupincluding H--, or a C₁ to C₁₀ straight- or branched-chain alkyl oralkenyl radical, a phenyl group, or a benzyl group, n is an integerbetween 0 and 30, inclusive, R₆ is a C₁ -C₂₀ alkyl or alkoxy group, andR₇ is a C₂ or C₃ alkyl group, said quaternary ammonium compound having awater content not greater than 1.2 percent.
 14. The compound as setforth in claim 13, wherein R₇ is --C₃ H₆ -- and R₆ is a combination ofapproximately equal amounts of C₁₂ -C₁₅ alkyl groups.
 15. A quaternaryammonium compound having the formula: ##STR24## wherein m is either 0,1, 2, or 3; each R₅ may be the same or different, and are selected fromthe groups including straight or branched-chain alkyl or alkenyl radicalhaving from 1 to 30 carbon atoms, inclusive, or a phenyl or benzylradical; R₂ is H--, a C₁ to C₁₀ straight- or branched-chain alkyl oralkenyl radical, a phenyl group, a benzyl group, or a halogenated alkylgroup; R₃ and R₄ are different or the same and are selected from thegroup including H--, or a C₁ to C₁₀ straight- or branched-chain alkyl oralkenyl radical, a phenyl group, or a benzyl group, and wherein n is aninteger between 0 and 30, inclusive made by the process of claim
 14. 16.The compound as set forth in claim 15, wherein R₅ is a straight-chainalkyl radical having from 1 to 18 carbon atoms.
 17. The compound as setforth in claim 16, wherein m is 2, and n is 0, and R₂ is H--.
 18. Thecompound as set forth in claim 16, wherein m is 3, each R₅ is CH₃ CH₂--, n is 0, and R₂ is CH₃.
 19. The compound of claim 1 containing lessthan about 0.1 percent water.
 20. The compound of claim 9 containingless than about 0.1 percent water.
 21. The compound of claim 13containing less than about 0.1 percent water.
 22. A method of making anethoxylated quaternary ammonium glycol borate ester, comprising blendingboric acid with an alkylene glycol so as to form an alkylene glycolborate ester; removing the majority of water from said alkylene glycolborate ester so that water remaining therein does not exceed 0.2% of thetotal weight of said alkylene glycol borate ester and said water; addingsaid alkylene glycol borate ester to a primary, secondary, or tertiaryamine so as to form an aminated alkylene glycol borate ester; andalkoxylating said aminated alkylene glycol borate ester with an alkyleneoxide in the presence of a solvent.
 23. A method of making anethoxylated quaternary ammonium glycol borate ester, comprising blendingboric acid with an alkylene glycol and heating the blend so as to forman alkylene glycol borate ester; removing the majority of water fromsaid alkylene glycol borate ester; adding said alkylene glycol borateester to a primary, secondary, or tertiary amine so as to form anaminated alkylene glycol borate ester; and alkoxylating said aminatedalkylene glycol borate ester with an alkylene oxide in the presence of asolvent.
 24. The method as set forth in claim 23, wherein the molarratio of said alkylene glycol to boric acid is between 1:1 and 3:1. 25.The method as set forth in claim 23, wherein said solvent comprises from5%-20% of the combined weight of said solvent, boric acid, alkyleneglycol, amine, and alkylene oxide.
 26. The method as set forth in claim23, wherein said solvent comprises from 5%-20% of the combined weight ofsaid solvent, boric acid, alkylene glycol, amine, and alkylene oxide.27. The method as set forth in claim 23, wherein the molar ratio of saidamine to said alkylene glycol borate ester is 1:0.75.
 28. The method asset forth in claim 23, wherein the molar ratio of said amine to saidalkylene glycol borate ester is 1:0.50.
 29. The method as set forth inclaim 26, wherein the molar ratio of said amine to said alkylene glycolborate ester is 1:0.75.
 30. The method as set forth in claim 26, whereinthe molar ratio of said amine to said alkylene glycol borate ester is1:0.50.
 31. The method as set forth in claim 30, wherein said solvent isdiethylene glycol.
 32. The method as set forth in claim 30, wherein saidsolvent is ethylene glycol.